Process for the manufacture of coloring-matters derived from gallocyanin.



UNITED STATES PATENT OFFICE.

ARNOLD S'JJIEIJSI'ER, OIE BASEL, SWITZERLAND, ASSIGNOR 'TO CHEMISCHE FABRIK- TORI [ADS SANDUZ, OF BASED, SWITZERLAND.

PROCESS FOR THE MANUFACTURE OF COLORING-MATTERS DERIVED FZROM GALLOCYiANIN.

{No Drawing.

guenin & Co., No. 231,316of 4 July, 1893,

(U Patent No.53l,148, December 18, 1.894,

lBierer and de la Harpe) mentions that the phenols and their derivatives react with the gallocyanins in the presence of mineral acids to form leuco derivatives'which by oxidation onthe fiber give bluer shades than those obtained with the gallocyanins themselves.

I have now found that newv p-roducts, different from the above mentioned bodies, are obtained upon operating in alkaline solution.

Among the phenolic derivatives which can be advantageously condensed with .gal locyanin'may be mentioned resorcin and its homologues, analogues and {substitution products and certain naphthol sulfonic acids, for example the beta naphthol sultonic acid of Schae'fier salt or R salt. The condensation of these bodies with ,gallocyanin is accompanied .by partial reduction of this dyestufi. I

In order to have a quantitative yield of thecondensation products I introducea suitable oxidizing agent during'the reaction, for example by passing a current otair into the alkaline solution. This method ofworking likewise allows of starting with leucogallocyanin. f

When the condensation is finished 1 heat themass during one or two hours. The color bases obtained are not soluble or only slightly soluble in water, and in order to bring them into .a suitable form for vprinting or dyeing it is necessary to reduce them. Chemically the dyestufls obtained according to the invention maybe regarded as derivatives of a pyrogallol,gallocyanin, the carboxyl group of the :gallocyanin being split 011 during the condensation in alkaline solution, Whereas the leuco-derivatives of the French Patent No. ,231316 contain the carboxyl group probably in the shape of anthone derivatives formed by elimination ofa molecule of water .betweenthe car- Specification of Letters Patent.

Patented May 16, 1911.

Application filed. May 22, 1909. SeriaI No. 497,682.

boXyl igroup of the gallocyanin and the molecule of resorcin.

The structural formula of the product of U. S? Patent No. 531 1 18 is probably:

HGlGHa whereas the product of the present applicap in case of the condensation of gallocyanin with resorcin.

T-he-leuco derivatives of the new coloring e matters are distinguished from the dilficultly soluble product of the French Patent No.

281,316 by" their high solubility in Water, which greatly. facilitates their employment in printing; moreover they yield on short steaming and without any subsequent oxidation, clear blue "or violet shades on chromium inordants, whereas the 'leuco derivatives of the said French patent are difficult to fix and egive gray-ish blue shades.

Ewample I .3 1 parts of thegallocyanin from nitrosodimethylanili-n and gallic acid are dissolved in 8 parts of caustic soda (2 25 to 34 parts of resorcin vare then added and the Whole is stirred for about three days at ordinary temperature in I the presence of a current of air passed through the solution. The latter gradually thickens to a crystalline pasty mass which is finally heated to 90 C. filtered and washed. The dried condensation product is crystalline powder with a bronze lust-er. It dissolves in concentrated sulfuric acid or concentrated hydrochloric acid with a pure blue color which on dilution with water changes to red-violet with gradual precipitation of a ditficultly soluble sulfate or hydrochlorid. The body dissolves with a violet-blue color in a hot solution of excess carbonate of soda or caustic soda; it is diflicultly soluble in alcohol with a blue color.

If in the above example the quantity of Water is increased to twice or thrice the amount, and at the same time the duration of reaction is shortened, there is obtained as the main product of the reaction and besides the above described body, a soda-salt which crystallizes in small leaves. On heating the blue aqueous solution of this salt to 90 (1., the above described condensation product separates in the form of a voluminous crystalline precipitate or in crystals having a brassy or coppery luster. l The said soda salt which is an intermediate product, gives with hydrochloric acid a green insoluble hydrochlorid which, on reduction yields a difficultly soluble yellow crystalline leuco derivative, which appears to be identical with that obtained by condensation of gallocyanin with resorcin in accordance with French Patent No. 231,316.

Example [[-GaZZ00yam'n and beta-naphtholsulfom'o a02'ds.To a solution of 67 parts of gallocyanin in 1000 parts of water and 80 parts of 20% caustic soda is added a slightly alkaline solution of 67 parts of sodium salt of Schaeffers beta-naphthol 6 sulfonic acid, and the mixture is heated for some hours at 6080 C. while passing a current of air therethrough. The blue solution obtained is poured into hot dilute hydrochloric acid. The condensation product separates in the form of a resinous substance having a coppery luster. The acid liquor is decanted and the residue is dissolved in ammonia. The dyestufi gives violet-blue shades on wool or chrome-mordanted cotton. In this example the Schaefi'er naphtholsulfonic acid may be replaced by an isomeric or analogue acid, capable of being condensed with gallocyanin, for example by It salt, which yields a dycstuif of identical shade but more soluble.

The products of which the preparation is described in the above examples may also be obtained if carbonate of soda or ammonia is used in place of the caustic soda. Similar products are also obtained if ordinary gallocyanin is replaced by its bisulfite derivative or by the gallocyanins derived from gallio ether or from gallamic acid, these latter being probably converted in the pres ence of heat and in an alkaline medium into gallocyanins of gallic acid.

The new dyestuft' obtainable according to the Example I is difficultly soluble in water; in order to bring it into a form suitable for dyeing or printing fabrics, it is necessary to convert it into its leuco derivatives, the hydrochlorids of which are readily soluble and are particularly suitable for printing cotton, on which they give, on short steaming, blue to violet shades, fast to washing.

The method of procedure may be as follows :--1 part of a product obtained according to Example I is suspended in 10 to 20 parts water to which 2% parts hydrochloric acid have been added. Zinc dust or other reducing agent capable of operating in acid solution is then slowly added, gently warming until solution occurs. The solution is filtered and salted out. The hydrochlorids of the leuco derivatives thus separate as thick oils very soluble in water; they can be dried in vacuo but it is simpler to use them in solution.

The reduction of the dyestuff can also be effected in an alkaline medium with the aid of sulfid of sodium or of hydrosulfites, or by means of electrolysis.

The leuco derivative corresponding to the product of Example I gives blue shades in printing.

What I claim and desire to secure by Letters Patent is 1. Process for the manufacture of dyestuffs, consisting in condensing gallocyanin with a phenolic derivative in alkaline solution.

2. Process for the manufacture of dyestufls, consisting in condensing gallocyanin with a phenolic derivative of the naphthalene series, in alkaline solution.

3. Process for the manufacture of dyestuffs, consisting in condensing gallocyanin, in alkaline solution, with a naphthol sulfonic acid.

4t. Process for the manufacture of a dyestuff consisting in condensing gallocyanin with Schaetfer salt, in alkaline solution.

5. Process for the manufacture of dyestuffs, consisting in treating gallocyanin in alkaline solution with a naphthol-sulfonic acid in presence of an air current.

6. Process for the manufacure of a dyestuft', consisting in treating gallocyanin in alkaline solution with Schaefler salt in the presence of an air current.

7. Process for the manufacture of dyestuffs, consisting in treating gallocyanin in alkaline solution with a phenolic derivative in the cold and in presence of an air current, and heating the product obtained.

8. Process for the manufacture of dyestufi's, consisting in treating gallocyanin in alkaline solution with a phenolic derivative of the naphthalene series in the cold and on chromium inordants pure blue to bluein presence of an air current, and heating the product obtained.

9. The herein described new dyestuifs being condensation products of gallocyanin with a phenolic derivative in which condensation products the carboxyl group is split off, and forming crystalline powders, dissolving in strong sulfuric. acid or hydro- 10 chloric acid with a blue color and yielding 1 Violet shades fast to light and soaping. t

In witness whereof, I have hereunto signed my name in the presence of two subscribing witnesses.

ARNOLD 'STEINER.

Witnesses GEORGE WAGNER, CHARLES RYHINER.

Copies of this patent may be obtained for five cents each, by addressing the Commissioner of Patents, Washington, D. G. 

